This invention relates to a process for rotomolding tetrafluoroethylene/perfluoro(alkyl vinyl ether) (TFE/PAVE) copolymer with pellets prepared by melt-extrusion.
Rotomolding, which as used here includes rotocasting and rotolining, is a melt-fabricable tetrafluoroethylene copolymer processing method especially suited for making large hollow articles in a heated rotating mold. In the case of rotocasting, after cooling of the mold, the hollow article is removed from the mold. In the case of rotolining, the hollow article remains as a lining for the mold. Thus, the mold can be a capped pipe tee, and the hollow article forms a lining for the tee. The rotomolding process is described in The Encyclopedia of Polymer Science and Engineering, Vol. 14, p. 659, John Wiley and Sons Inc., New York, 1988. Polymer for rotomolding is in the form of powder, sometimes called beads or granules, of roughly spherical shape. Although particle sizes up to 3000 xcexcm are disclosed in the literature, in practice, the particle sizes are typically less than about 500 xcexcm in size. Conventional standard melt-extruded polymer cubes, sometimes called pellets of the sort used as a feed for melt extrusion or injection molding have not been suitable for rotomolding, because the resultant rotomolded article has a rough interior, uneven thickness and contains bubbles within its thickness. In an attempt to avoid these deficiencies, rotomolding powder has been made by other processes, such as agglomerating polymer particles obtained from polymerization into granules as disclosed in U.S. Pat. No. 4,714,756 relating to the preparation of tetrafluoroethylene/perfluoro(alkyl vinyl ether) (TFE/PAVE) copolymer rotomolding powder. Because polymers such as TFE/PAVE are used both in melt extrusion and in rotomolding, and these require the polymer to be in different forms, separate polymer preparation processes and equipment must be maintained. Furthermore, powders must be classified to remove fines or dust. Settling and segregation in storage and shipping may require remixing to ensure uniform size distribution. Static electricity can make handling difficult. In other words, while the use of powder instead of melt-extruded cubes for rotomolding has produced a better rotomolded product, the use of the powder has had the disadvantage of increasing expense.
There is a need for a rotomolding process that does not require the use of polymer in powder form.
The present invention satisfies this need by providing smaller size melt-extruded cubes of melt-fabricable TFE copolymer. In particular the size range of the xe2x80x9cminicubesxe2x80x9d is that at least 80% are in the range of 200 to 1200 xcexcm.
The process of the present invention is carrying out the rotomolding using these copolymer minicubes to form a hollow article of the copolymer.
Melt-fabricable TFE copolymer used in the present invention is preferably partially crystalline, and the preferred comonomers are at least one monomer selected from the group consisting of perfluoroolefin having 3 to 6 carbon atoms, preferably hexafluoropropylene (HFP); olefins, preferably ethylene and propylene, more preferably ethylene; and perfluoro(alkyl vinyl ether) (PAVE), wherein the alkyl group contains 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms. The more preferred copolymers are perfluorinated. Among the perfluorinated copolymers are terpolymers of TFE/HFP/perfluoro(ethyl vinyl ether), such as that disclosed in U.S. Pat. No. 5,677,404. The most preferred copolymers are TFE/PAVE copolymers such as disclosed in U.S. Pat. No. 3,528,954. Preferred forms of TFE/PAVE copolymers are disclosed in U.S. Pat. No. 5,760,151, wherein the perfluoroalkyl group is ethyl (PEVE), and the copolymer contains at least about 3 wt %, preferably at least about 5 wt %, and more preferably at least about 7 wt % of the PVE comonomer, preferably the PEVE copolymer. The PEVE copolymers are called TFE/PEVE copolymers.
The rotomolding process involves the steps of feeding the copolymer minicubes described above to the hollow mold, rotating the mold, heating the mold while it is rotating, the temperature being above the melting point of the copolymer, with the heating and rotating being carried out for sufficient time for the minicubes to fuse together in the interior shape of the mold to form a hollow article conforming to this interior shape, and cooling the mold and the article contained in it. The rotation of the mold causes the minicubes to tumble over one another and the heating of the mold eventually causes these minicubes to soften, flow, and then fuse together. The only force exerted upon these minicubes is the centrifugal force resulting from rotation. The rotation of the mold is multiaxial, so that the entire exposed interior surface of the mold is covered with the molten copolymer. It is therefore important that the copolymer be sufficiently flowable at the temperature used so as to form the molded hollow article. Thus, the melt flow rate (MFR) of the copolymer is preferably in the range of about 2 to about 100 (g/min), more preferably about 5 to about 50, and even more preferably about 10 to about 5.
The melt-extruded particle described in this invention is referred to hereinafter as xe2x80x9cminicubexe2x80x9d, although as will be shown, it is not cubic in shape. Minicube is made by melting the TFE copolymer in a single screw or twin screw extruder, and extruding the melted polymer through a multihole die to yield minicubes in the form of small cylinders approximately 200 to 1200 xcexcm in diameter, preferably about 500 to about 1200 xcexcm in diameter, and melt-cutting the copolymer as it exits the die into lengths of about 200 to about 2000 xcexcm, preferably about 500 to about 1500 xcexcm. It has been found however, that cutting to these short lengths also produces longer cubes, e.g. up to 3000 xcexcm, in a minor proportion ( less than 30%). The small diameter of the minicubes, however, still enables the melt-extruded cubes to have an overall small size as determined by sieving as described hereinafter. The minicubes, insofar as dimensions are concerned, are used in the rotomolding process as-extruded and cut into lengths; they are unground, i.e. they are not subjected to comminution to smaller sizes.
To reduce the effect of shear on melted polymer, it has been found useful to put a melt pump, an example of which is a gear pump, between the extruder and the die. By this means, the pressure necessary to extrude the melt through the die is generated by the melt pump, in which shear forces are less than would be experienced if the extruder alone were used to generate the necessary pressure. Excessive shear can cause copolymer degradation and thus adversely affect copolymer properties. An example of a suitable die is one having about 700 holes (extrusion orifices), each about 30 mils (760 xcexcm) in diameter. Because of the phenomenon known as xe2x80x9cdie swellxe2x80x9d or xe2x80x9cextrudate swellxe2x80x9d, the minicubes so produced have a larger diameter than the extrusion orifices, whereby for a given minicube diameter and orifice selected to provide such diameter, there will be some variation in the minicube diameters obtained. The cylindrical shape of the minicubes may also vary, from perfect cylinders to cylinders having slightly flattened sides or elliptical cross-section. The diameter of the minicube is considered to be the longest dimension normal, i.e. perpendicular, to the length of the minicube.
The 760 xcexcm diameter orifice provides minicubes having an average diameter of about 1000 xcexcm. The extrudate is cut into short lengths. One means of doing this is through use of a conventional cutter operating across the outer face of the extrusion die, the cut minicubes falling into water for cooling. The preferred length is in the range of about 200 to about 2000 xcexcm, more preferably about 500 to about 2000 xcexcm. There will also be some variation in the minicube length for a given cutting length. The variability of the minicube diameter and length is greater than for the melt extrusion of standard size cubes, and it has been found that this greater size variability of the minicubes compared is an advantage in rotomolding applications, by providing much smooth, bubble-free hollow articles of more uniform cross-section (wall thickness) in the rotomolding process. It is believed that the broader size distribution contributes to better packing of the minicubes on the surface of the mold, although the tumbling of the minicubes prior to fusing together distinguishes this packing effect from packing systems where no rotation or heating to melt is involved. Minicubes should have a variability, as measured by the coefficient of variation (as hereinafter defined) of their weight, length, width, or height, of at least about 25%, preferably at least about 35%, more preferably at least about 45%, and most preferably at least about 50%.
For comparison, the standard die for making conventional cube uses a 25 to 200 hole die, the holes of which are about 2500 xcexcm (100 mils) in diameter, and produces cleanly cut cubes ranging from about 3000 to about 4000 xcexcm in diameter, about 1000 to about 2000 xcexcm in length, and of regular geometry, i.e. they are right cylinders.
The size of the minicubes of the present invention can be measured by screening, in which case either the minicube diameter or length may be small enough for the minicube to pass through a given screen size, while the screen which retains the minicubes will have apertures generally larger than either the diameter of length of the minicube. However the minicube size range is set, there may be some variation of length or diameter outside of this range because of the variability in the diameters and lengths of the minicubes made under the same conditions, together with the variability resulting from screen sizing. Thus for a given size range, 20% or less of the minicubes will be slightly outside of this range. The preferred size range for the minicubes of the present invention is about 500 to about 1200 xcexcm, more preferably about 600 to about 1000 xcexcm, wherein at least about 90% of the minicubes are within this range and, even more preferably, about 850 to about 1000 xcexcm wherein at least at least about 70%, more preferably at least about 80%, of the minicubes fall within this range. The minicube diameter is the limiting dimension for the minicube size range. If the diameter is small enough, the minicube will pass through the screen having openings slightly greater than the maximum size desired. In that case, the minicube length can be greater than these screen openings and the minicubes will still pass through the openings because of the small diameters of the minicubes.
With respect to the desired stability of the TFE copolymer used in the present invention, it is known in the art that fluoropolymers can contain unstable end groups such as xe2x80x94COOH, xe2x80x94CH2OH, xe2x80x94CO2CH3, xe2x80x94COF, and xe2x80x94CFxe2x95x90CF2 depending on ingredients used in the polymerization process used to make the TFE copolymer (U.S. Pat. No. 4,675,380). These unstable end groups are thermally and/or hydrolytically unstable. This is what is meant by the term xe2x80x9cunstable end groupsxe2x80x9d. They have a tendency to cause bubbles or voids upon melt fabrication. These voids can be detrimental to the physical or electrical properties of fabricated articles. Because melt processing can increase the concentration of unstable end groups in perfluoropolymers, it is preferred to fluorinate the minicubes made from such polymers according to this invention before using them in rotomolding applications. The unstable end group concentration in the polymer making up the minicubes should be less than about 80, preferably less than about 10, more preferably less than 6 unstable end groups per million carbon atoms in the polymer. Unstable end group identity and measurement is disclosed in U.S. Pat. No. 4,743,658 as is the process for fluorination which is applied to the minicubes of the present invention in the same manner as disclosed for the granules in the patent.
Copolymers of this invention that are not perfluorinated, for example the copolymer of TFE and ethylene (ETFE), can be processed at lower temperatures where the decomposition rates of the unstable end groups described above are slower and the resulting defects in the molded article are fewer or not present at all. An indication of the processibility of ETFE at lower temperatures than are possible with perfluoropolymers is seen in ASTM D 1238. ETFE flow rates are measured at 297xc2x0 C. in the standard extrusion plastometer (melt indexer), while perfluoropolymers such as TFE/HFP (FEP) and TFE/PAVE (PFA) are measured at 372xc2x0 C.
Particle size is determined according to ASTM D 1921-96. Sieves selected from U.S. Standard Sieves Nos. 14, 16, 18, 20, 30, 35,40, 50, and 60 are used for the minicube samples. Sieve Nos. 20, 25, 30, 35, 40, 45, and 50 are used for the rotomolding powder sample. The sieves are assembled so that the size of the openings decrease in sequence from the top of the stack. A pan is placed at the bottom to collect material that passes through the sieve with the smallest openings. A 40 to 60 g or greater representative portion of the sample is weighed out to the nearest 0.01 g, and placed in the top sieve. The stack of sieves is placed on a mechanical shaker. The shaker is run for approximately 10 minutes. After shaking, the amount of material retained on each sieve and in the pan is determined to the nearest 0.01 g. The distribution of sample among the sieves and the pan is reported as a percentage of the total sample sieved. The distribution is tabulated versus the size of the opening in the sieve screen. Mean particle size is calculated according to ASTM D 1921-96 xc2xa713.
The size range is defined as the range between the sieve opening through which the minicubes pass and the sieve opening through which the minicubes do not pass. For example, if, following the sieving procedure of ASTM D 1921, 80% by weight of a representative sample of a lot of minicubes were found to pass through a sieve with openings of 1200 xcexcm and to be retained on a sieve with openings of 200 xcexcm, one would say that 80 wt. % of that lot of minicubes is in the size range of 200 to 1200 xcexcm.
Melt flow rates (MFR) are determined by ASTM D 1238-52T modified as described in U.S. Pat. No. 4,380,618. MFR is reported in units of g/10 minutes. Temperature is 372xc2x0 C. for perfluoropolymers, 297xc2x0 C. for ETFE polymer.